Organic halides are very important building blocks in organic synthesis. However, in their application in the past, expensive but relatively active organic bromides and iodides were used in coupling reactions to synthesize target molecules (Chem. Rev. 1994, 94, 1047). If inert carbon-chlorine bonds can be selectively activated and to use cheap chlorides in these types of reactions, it would be much better not only in respect of atom economy but also in respect of industrial cost. So far, some organic phosphine ligands can be used to activate inert carbon-chlorine bonds (Angew. Chem. Int. Ed. 2002, 41, 4176; Acc. Chem. Res. 2007, 40, 275; Acc. Chem. Res. 2007, 40, 676; Acc. Chem. Res. 2008, 41, 1461; Eur. J. Org. Chem. 2008, 2013; Angew. Chem. Int. Ed. 2008, 47, 6338). However, during the study on the carbon-chlorine bond coupling reactions of the optically active β-chloro-α,β-unsaturated five-membered lactones, the inventor of the current invention has discovered that some ligands commonly used in the activation of carbon-chlorine bonds (such as: tricyclohexylphosphonium tetrafluoroborate or 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl etc.) cannot yield the corresponding optically active coupling products highly selectively (please see embodiments for specific examples).